EP2970744B1 - Synergistische wirkung von co-tensiden auf die rheologische leistung von bohr-, komplettierungs- und frakturierungsflüssigkeiten - Google Patents

Synergistische wirkung von co-tensiden auf die rheologische leistung von bohr-, komplettierungs- und frakturierungsflüssigkeiten Download PDF

Info

Publication number
EP2970744B1
EP2970744B1 EP14709645.7A EP14709645A EP2970744B1 EP 2970744 B1 EP2970744 B1 EP 2970744B1 EP 14709645 A EP14709645 A EP 14709645A EP 2970744 B1 EP2970744 B1 EP 2970744B1
Authority
EP
European Patent Office
Prior art keywords
fluid
viscoelastic
surfactant
alkyl
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP14709645.7A
Other languages
English (en)
French (fr)
Other versions
EP2970744A1 (de
Inventor
Lingling Li
James F. Gadberry
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nouryon Chemicals International BV
Original Assignee
Akzo Nobel Chemicals International BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Akzo Nobel Chemicals International BV filed Critical Akzo Nobel Chemicals International BV
Publication of EP2970744A1 publication Critical patent/EP2970744A1/de
Application granted granted Critical
Publication of EP2970744B1 publication Critical patent/EP2970744B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/035—Organic additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/72—Eroding chemicals, e.g. acids
    • C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/25—Methods for stimulating production
    • E21B43/26—Methods for stimulating production by forming crevices or fractures
    • E21B43/27—Methods for stimulating production by forming crevices or fractures by use of eroding chemicals, e.g. acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/30—Viscoelastic surfactants [VES]

Definitions

  • the present invention relates to the drilling, completion and stimulation of hydrocarbon-containing formations. More specifically, the invention relates to the viscoelastic surfactant based fluids and methods for utilizing same in gravel packing, cleanup, drilling and fracturing in a subterranean formation.
  • Viscoelastic fluids play a very important roles in oilfield applications.
  • the viscosity allows the fluids to carry particles from one place to another.
  • the drilling fluid is able to carry the drilling cuts from the wellbore to the surface.
  • Viscous fluids also play an essential role in gravel packing completion.
  • gravel pack operations a steel screen is placed in the wellbore and the viscous completion fluid places prepared gravel of a specific size in the surrounding annulus to minimize the sand production.
  • Fracturing fluids are also required to be viscous enough.
  • a hydraulic fracture is formed by pumping the fracturing fluid into the wellbore at a rate sufficient to increase pressure downhole to exceed that of the fracture gradient of the rock.
  • the fracturing fluid contains the proppant, which keeps an induced hydraulic fracture open after the pressure is released. Therefore it is important for the fluid to have enough viscosity to transport the proppant into the fracture.
  • VES viscoelastic surfactants
  • VES-based fluids have excellent capacity to suspend and transport sand/proppant.
  • VES fluids have several distinctive advantages over polymer-based fluids. Unlike polymer fluids, the VES based fluids are solid free, which minimize the formation damage after they break.
  • many viscoelastic surfactants are very sensitive to high concentrated brines. They don't often gel the heavy brines or the fluid viscosity is not stable under high temperature conditions.
  • viscoelastic fluids have some limitations for drilling, completion and fracturing applications, especially for deep wells, because many deep wells have bottom hole temperatures of 149 °C (300°F) or more, and they require heavy fluids to balance the well pressure and maintain control of the well.
  • VES packages such as VES/low MW polymer, cationic/anioinic surfactants and VES/cosurfactant can successfully viscosify moderate density brines (like CaCl 2 , CaBr 2 and NaBr brine).
  • moderate density brines like CaCl 2 , CaBr 2 and NaBr brine.
  • none of them can work in heavy ZnBr 2 brine at temperatures above 121 °C (250 °F) under normal dosage (equal or less than 6 vol% as received).
  • the ZnBr 2 brine and the mixed brine made by ZnBr 2 /CaBr 2 /CaCl 2 will be used if a density of 1.8 g/cm3 (15 ppg) or higher is needed for deep wells to balance the well pressure.
  • U.S. Patent Application Publication No. 2002-0033260 describes a high brine carrier fluid having a density of > 1.3 g/cm3 (10.8ppg) contains a component selected from organic acids, organic acid salts, and inorganic salts; a cosurfactant that may be sodium dodecylbenzene sulfonate (SDBS), sodium dodecylsulfate (SDS) or a mixture of two, or a hydroxyethylaminocarboxylic acid; and a zwitterionic surfactant, preferably a betaine, most preferably an oleyl betaine. It is indicated that zinc halides are not preferred, especially zinc bromide. In the examples, the heaviest brine that a useful viscosity was maintained in was at a density of 1.64 g/cm3 (13.7ppg). The highest working temperature is 138°C (280°F).
  • US2012/024529 A1 describes oil well treatment fluids comprising a viscoelastic surfactant and a water soluble polymer. Certain quaternary ammonium compounds are suggested for foamed treatement fluids. Compositions as claimed are not disclosed or suggested.
  • US 2008/277112 A1 describes a wellbore treatment fluid comprising a chelating agent and a viscosifying agent which can be a viscoelastic surfactant.
  • a chelating agent which can be a viscoelastic surfactant.
  • a viscosifying agent which can be a viscoelastic surfactant.
  • US2012/285694 describes an enhanced oil recovery process using a foaming composition wherein a foam stabilizer is used that is a alkyl dimethyl betaine, alkyl amidopropyl hydroxyl sulfobetaine, alkyl hydroxy sulfobetaine, or mixtures thereof.
  • a cationic polymer or surfactant may be used as an additional component.
  • Compositions as claimed are not disclosed or suggested.
  • U.S. Patent No. 7,148,185 B2 describes the surfactant fluid gels that are stable to brines having densities above about 1.56 g/cm3 (13ppg) at high temperatures.
  • the well treatments fluids contain a surfactant, preferably erucylamidopropyl betaine, and an amount of alcohol, preferably methanol, and a salt or mixture of salts of a divalent cation or mixture of divalent cations forming a brine, preferably one or more of bromide and/or chlorides of calcium and/or zinc.
  • Cosurfactants such as sodium dedecylbeneze sulfonate (SDBS) can also be used.
  • SDBS sodium dedecylbeneze sulfonate
  • the concentration of surfactant, BET-E-40, shown in the most of examples in heavy brines are 10%.
  • the VES fluid/fluid system of the present invention addresses the problem that drilling and production engineers have had for years. More particularly, the VES based fluid system of the invention exhibits significantly improved viscosity in high-density brines at elevated temperatures (>149 °C (300 °F)).
  • the present invention generally relates to viscoelastic surfactant based fluids and methods for utilizing same in various oilfield applications including, but not limited to, gravel packing, cleanup, drilling, acidizing and fracturing operations.
  • the viscoelastic fluid of the invention with a density greater than 1.14 g/cm3, comprises at least one amphoteric surfactant and at least one synergistic co-surfactant that increases the gel strength and extends the brine tolerance of said viscoelastic-based fluid.
  • the present invention relates to a VES fluid system that exhibits significantly improved viscosity in high-density brines, with a density greater than 1.14 g/cm3, at elevated temperatures (149 °C (>300 °F)). Numerous rheological experiments have been run to show the excellent viscoelasticity in heavy ZnBr 2 brine (1.98 g/cm3 (16.5 ppg)) up to 204 °C (400 °F), at a shear rate of 100 s -1 and pressure of 2758 kPa (400psi). Sand settling tests have been conducted at ambient temperature and high temperatures to show the excellent sand suspension properties of this new VES system. VES fluid system of the invention also has an extremely low (-15 °C) pour point, which solves the handling and transportation issues in cold regions.
  • the thickened compositions of the present invention can usefully be employed in methods of stimulating and/or modifying the permeability of underground formations, in drilling fluids, completion fluids, workover fluids, acidizing fluids, gravel packing, fracturing and the like. Additionally, the thickened compositions of the present invention can also be employed in cleaning formulations, water-based coatings, detergent formulations, personal care formulations, water based asphalt formulations and the like.
  • Viscoelasticity is a desirable rheological feature in drilling fluids, workover or completion fluids, and stimulation fluids which can be provided by fluid modifying agents such as polymeric agents and surfactant gelling agents.
  • Viscoelastic fluids are those which exhibit both elastic behavior and viscous behavior. Elasticity is defined as an instant strain (deformation) response of a material to an applied stress. Once the stress is removed, the material returns to its undeformed equilibrium state. This type of behavior is associated with solids. On the other hand, the viscous behavior is defined as a continuous deformation resulting from an applied stress. After a while, the deformation rate (shear rate or strain rate in general) becomes steady. Once the stress is removed, the material does not return to its initial undeformed state.
  • Viscoelastic fluids may behave as a viscous fluid or an elastic solid, or a combination of both depending upon the applied stress on the system and the time scale of the observation. Viscoelastic fluids exhibit an elastic response immediately after the stress is applied. After the initial elastic response, the strain relaxes and the fluid starts to flow in a viscous manner. The elastic behaviour of fluids is believed to aid significantly in the transport of solid particles.
  • the viscosity of a viscoelastic fluid may also vary with the stress or rate of strain applied. In the case of shear deformations, it is very common that the viscosity of the fluid drops with increasing shear rate or shear stress. This behavior is usually referred to as "shear thinning". Viscoelasticity in fluids that is caused by surfactants can manifest itself shear thinning behavior. For example, when such a fluid is passed through a pump or is in the vicinity of a rotating drill bit, the fluid is in a high shear rate environment and the viscosity is low, resulting in low friction pressures and pumping energy savings. When the shearing stress is abated, the fluid returns to a higher viscosity condition.
  • the elastic component of a viscoelastic fluid may also manifest itself in a yield stress value. This allows a viscoelastic fluid to suspend an insoluble material, for example sand or drill cuttings, for a greater time period than a viscous fluid of the same apparent viscosity. Yield stresses that are too high are not a good thing in drilling, as it may make restarting the drilling bit very difficult and causes a condition called "stuck pipe".
  • the fluid system of the invention comprises an effective amount of at least one viscoelastic surfactant and an effective amount of at least one synergistic cosurfactant.
  • the viscoelastic surfactant is an amphoteric surfactant that has the general formula (I): wherein R 1 is a saturated or unsaturated, hydrocarbon group of from about 17 to about 29 carbon atoms, in another embodiment from about 18 to about 21 carbon atoms.
  • R 1 is a fatty aliphatic derived from natural fats or oils having an iodine value of from about 1 to about 140, in another embodiment from about 30 to about 90, and in still another embodiment from 40 to about 70.
  • R 1 may be restricted to a single chain length or may be of mixed chain length such as those groups derived from natural fats and oils or petroleum stocks.
  • R 2 and R 3 are each independently selected from a straight chain or branched, alkyl or hydroxyalkyl group of from 1 to about 6 carbon atoms, in another embodiment, of 1 to 4 carbon atoms and still another embodiment from 1 to 3 carbon atoms.
  • R 4 is selected from H, OH, alkyl or hydroxyalkyl groups of from 1 to about 4 carbon atoms; preferably ethyl, hydroxyethyl, OH or methyl.
  • k is an integer of from 2-20, in another embodiment 2-12, and in still another embodiment 2-6, and in yet and in still another embodiment 2-4;
  • m is an integer of from 1-20, in another embodiment 1-12, and in still another embodiment 1-6, and in still another embodiment 1-3; and
  • n is an integer of from 0-20, in another embodiment 0-12, and in still another embodiment 0-6, and in still another embodiment 0-1.
  • the concentration of viscoelastic composition in the fluid is generally from about 0.5% to about 10%, in another embodiment from about 2% to about 8%, and in yet another embodiment from about 3% to about 5% by weight.
  • the viscoelastic surfactants disclosed and described herein are surfactants that can be added singly or they can be used as a primary component in the aqueous, thickened compositions of the present invention.
  • examples of the viscoelastic surfactants contemplated by the present invention include, but are not limited to, erucamidopropyl hydroxypropyl sulfobetaine, erucamidopropyl hydroxyethyl sulfobetaine, erucamidopropyl hydroxymethyl sulfobetaine, and combinations and mixtures thereof.
  • Armovis EHS an erucamidopropyl hydroxypropylsultaine, can be beneficially employed and is available from AkzoNobel, Chicago, Illinois.
  • viscoelastic surfactant is the surfactant of Formula (I) where R 1 is unsaturated 21 carbon chain, R 2 and R 3 are methyl group, R 4 is hydroxyl group, k equals 3, both m and n are 1.
  • the synergistic co-surfactant increases the gel strength of the viscoelastic-based fluid and extends the brine tolerance. It has the general structure (II) wherein R 1 is a saturated or unsaturated, hydrocarbon group of from about 12 to about 22 carbon atoms. R 2 , R 3 and R 4 are each independently selected from a straight chain or branched, alkyl or hydroxyalkyl group of from 1 to about 4 carbon atoms; and a hydroxyl group.
  • the concentration of the cosurfactant in the fluid is from about 0.1 wt% to about 4%; In another embodiment, the concentration of the cosurfactant in the fluid is about 0.5 wt% to about 1.5 wt%.
  • the ratio of surfactant to synergistic co-surfactant is generally from about 1:1 to about 15:1; in another embodiment from about 2:1 to 15:1; in still another embodiment from 3:1 to about 15;1, and in yet another embodiment from 3:1 to about 10:1.
  • co-surfactants include, but are not limited to, Arquad T/50 and Ethoquad E/12-75, both of which are available from AkzoNobel, Chicago, Illinois.
  • co-surfactants include, but are not limited to, a cationic surfactant of Formula (II) where R 1 is unsaturated 18 carbon chain, R 2 , R 3 and R 4 is hydroxyl groups; and a cationic surfactant of Formula (II) where R 1 is unsaturated 22 carbon chain, R 2 , R 3 are ethylhydroxy groups and R 4 is methyl group.
  • High density brines with a density greater than 1.14 kg/I, for oilfield use are usually made from salts of divalent cations such as calcium and zinc. Brines made from potassium, ammonium, sodium, cesium and the like may be used as well. Organic cations such as tetramethylammonium can also be employed. Typical inorganic anions for high density brines are chloride and bromide. Organic anions such as formate and acetate may be used. Some combinations of these anions and cations may have to be used to give higher density brines. The selection of one salt over the other or two salts over single salt typically depends on environmental factors.
  • a single salt fluid may work during the heat of the summer, whereas during coolertemperatures a two salt fluid may be required due to its lower Truce Crystallization Temperature (TCT), i.e., the temperature at which crystalline solids begin to form when cooled.
  • TCT Truce Crystallization Temperature
  • the viscoelastic fluid/well stimulation fluid according to the present invention has quite a high density.
  • the viscoelastic fluid/well stimulation fluid according to the present invention has a density of greater than 1.14 g/cm3 (9.5 ppg); in another embodiment, greater than 1.17 g/cm3 (9.8 ppg); in yet another embodiment, greater than 1.38 g/cm3 (11.5 ppg).
  • the viscoelastic fluid/well stimulation fluid according to the present invention has a density of 2.3 g/cm3 (19.2 ppg) or less; in another embodiment, 1.98 g/cm3 (16.5 ppg) or less.
  • the range of density of the viscoelastic fluid/well stimulation fluid according to the present invention may be greater than 1.14 g/cm3 (9.5 ppg) to 2.3 g/cm3 (19.2 ppg) or less, preferably, greater than 1.17 g/cm3 (9.8 ppg) to 1.98 (16.5) or less.
  • the viscoelastic surfactant used in the examples is Armovis EHS, available from AkzoNobel.
  • the co-surfactants used in the examples are cationic cosurfactant A and cationic cosurfactant B.
  • Cosurfactant A is Arquad T/50, a cationic surfactant based on tallow amine (Tallowtrimethylammonium chloride).
  • Cosurfactant B is Ethoquad E/12-75, an erucyl amine (2) ethoxylate, quarternary ammonium salt. Both cosurfactants are available from AkzoNobel.
  • FIG. 1 Shown in Figure 1 is a graph of the effect of cosurfactant A on the viscosity of Armovis EHS in 1.38 g/cm3 (11.5ppg) CaCl2. It was observed that the viscosity at low temperatures was significantly increased with the addition of cosurfactant A. The performance at high temperatures was still excellent up to 177 °C (350F). The viscosity reading was 132 mPas (cp) at 177 °C (350F) at 100s -1 . The results are shown in Figure 1 .
  • Figure 2 shows the results of viscosity with and without the addition of cosurfactant A in 1.5 g/cm3 (12.5ppg) NaBr.
  • the low temperature performance was increased dramatically after the addition of cosurfactant A, and the viscosity maintained the viscosity above 100 mPas (cp) up to 166 °C (330°F).
  • Figure 5 shows the results of viscosity at various shear rates after the addition of cosurfactant B in 1.7 g/cm3 (14.2ppg) CaBr2 at different temperatures. Obviously, the surfactant in brine behaved as shear-thinning non-Newtonian fluid. The high viscosity at low shear rate indicates the high elasticity of the fluid, over the temperature band of 10-149 °C (50-300F).
  • FIG. 7 Shown in Figure 7 is a graph showing the comparison between two surfactant systems in 1.81 g/cm3 (15.1ppg) ZnBr2/CaBr2. It can be seen that there is huge difference with and without the use of cosurfactant B.
  • the maximum working temperature in this particular brine is 121 °C (250°F).
  • chloride salt plays an important role in extending the temperature upper limit of surfactants.
  • the surfactants were blended in 20% CaCl2 (about 1.17 g/cm3 (9.8 ppg)) to make the gel, in the same way as described in Examples 1 to 7. Then the gel was put in the refrigerator.
  • the Grace M5600 Rheometer was used for the measurements. The rheometer was pre-cooled from room temperature by using 1:1 ethylene glycol/water as coolant circulator. After the sample was put on the rheometer and the temperature reached 2.2 °C (36F), the sample was rotated at a shear rate of 900 s -1 for 2 min. Then the rheometer was stopped and restarted immediately with a lower shear rate (100s -1 for Fig 8 and 1 s -1 for Fig 9 ). The changes in viscosity with time were recorded.
  • FIGs 8 and 9 show how long it took EHS /cosurfactant A system for viscosity recovery in 20% CaCl2 at 2.2 °C (36°F) (100s -1 for Fig 8 and 1 s -1 for Fig 9 ). Usually, the lower temperature, the longer recovery time needed. The results indicate that it only took the blend system 10-15 seconds to have viscosity climb up after changing the shear rate.
  • Sand settling tests were done in 500 ml graduate cylinder.
  • 550 ml of the test fluid was prepared using the same mixing procedures as Examples 1-7. Amount of sand (0.7 g/cm3 (6 pound per gallon)) and test fluid to make a total slurry volume of 550 ml were calculated and measured, and then the proppant was added into the bottle containing the test fluid. The whole mixture was shaken vigorously until the proppant was evenly dispersed. Once the slurry was prepared, it was poured into the 500 ml graduated cylinder. Volume of cleared liquid was recorded over a two hour period at room temperature. Then the cylinder was placed in the oven at 82 °C (180 °F) and preheated for 2 hours before the high temperature test began. It should be noted that several times of vigorous shake may be necessary during 2 hours of preheat.
  • Table 1 summaries the results of sand settling test in 1.7 g/cm3 (14.2ppg) CaBr2 containing 6% EHS/Cosurfactant B. At ambient temperature and 82 °C (180°F), almost no sand settling was observed. Table 1 6% 3:1 EHS/Ethoquad E/12-75 in 1.7 g/cm3 (14.2ppg) CaBr2 RT 82 °C (180F) Time (min) volume cleared (ml) 0 0 0 5 0 0 10 0 0 15 0 0 20 0 0 25 0 0 30 0 0 0 45 0 0 0 60 0 0 75 0 0 90 1 0 105 1 ⁇ 1 120 1 ⁇ 1
  • the sand settling test was also conducted in 1.8 g/cm3 (15ppg) CaBr2 viscosified by 6% EHS/Cosurfactant B. Table 2 shows that almost no sand settled down at 82 °C (180°F), but it did at room temperature. The total volume that was cleared out after 30 min was 79ml, which was 14.4% of total volume. Shown in Figure 11 are some photos of sand settling. Compared to Example 10, it has been found out that heavier brine has less capability to suspend the sand at low temperatures.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mining & Mineral Resources (AREA)
  • Geology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Environmental & Geological Engineering (AREA)
  • Fluid Mechanics (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Detergent Compositions (AREA)
  • Lubricants (AREA)
  • Cosmetics (AREA)

Claims (15)

  1. Viskoelastisches Fluid, umfassend wenigstens ein viskoelastisches Tensid und wenigstens ein synergistisches Co-Tensid, wobei das viskoelastische Tensid ein amphoteres Tensid der folgenden allgemeinen Formel (I) ist:
    Figure imgb0007
     wobei R1 eine gesättigte oder ungesättigte Kohlenwasserstoffgruppe mit 17 bis 29 Kohlenstoffatomen ist, R2 and R3 jeweils unabhängig ausgewählt sind aus einer geradkettigen oder verzweigten Alkyl- oder Hydroxyalkylgruppe mit 1 bis 6 Kohlenstoffatomen, R4 ausgewählt ist aus H, OH, Alkyl- oder Hydroxyalkylgruppen mit 1 bis 4 Kohlenstoffatomen; k eine ganze Zahl von 2-20 ist, m eine ganze Zahl von 1-20 ist und n eine ganze Zahl von 0-20 ist,
    und das synergistische Co-Tensid die folgende allgemeine Struktur (II) hat:
    Figure imgb0008
     wobei R1 eine gesättigte oder ungesättigte Kohlenwasserstoffgruppe mit 12 bis 22 Kohlenstoffatomen ist, R2, R3 und R4 jeweils unabhängig ausgewählt sind aus einer geradkettigen oder verzweigten Alkyl- oder Hydroxyalkylgruppe mit 1 bis 4 Kohlenstoffatomen und einer Hydroxylgruppe,
    wobei das viskoelastische Fluid eine Dichte von mehr als 1,14 g/cm3 hat.
  2. Viskoelastisches Fluid nach Anspruch 1, wobei in der allgemeinen Formel (I) R1 eine fettaliphatische Gruppe ist, abgeleitet aus natürlichen Fetten oder Ölen mit einer Jodzahl von etwa 1 bis 140, vorzugsweise einer Jodzahl von 30 bis 90, weiter bevorzugt einer Jodzahl von 40 bis 70.
  3. Viskoelastisches Fluid nach Anspruch 2, wobei in der allgemeinen Formel (I) R1 eine fettaliphatische Gruppe ist, abgeleitet aus natürlichen Fetten, Ölen oder Erdölvorräten mit einer einzelnen Kettenlänge oder einer gemischten Kettenlänge, wobei die natürlichen Fette und Öle oder Petroleumvorräte ausgewählt sind aus Talgalkyl, gehärtetem Talgalkyl, Rapsölalkyl, gehärtetem Rapsölalkyl, Tallölalkyl, gehärtetem Tallölalkyl, Cocoalkyl, Oleyl, Erucyl, Sojaalkyl oder ihren Kombinationen und/oder Mischungen.
  4. Viskoelastisches Fluid nach einem der Ansprüche 1-3, wobei in dem viskoelastischen Tensid der allgemeinen Formel (I) R1 eine ungesättigte Alkylgruppe mit 21 Kohlenstoffatomen ist, R2 und R3 Methylgruppen sind, R4 eine Hydroxylgruppe ist, k gleich 3 entspricht und m und n gleich 1 sind.
  5. Viskoelastisches Fluid nach einem der Ansprüche 1-4, wobei das viskoelastische Tensid der allgemeinen Formel (I) ausgewählt ist aus Erucamidpropyl-Hydroxypropyl-Sulfobetain, Erucamidpropyl-Hydroxyethyl-Sulfobetain, Erucamidpropyl-Hydroxymethyl-Sulfobetain und ihren Kombinationen und Mischungen.
  6. Viskoelastisches Fluid nach einem der Ansprüche 1-5, wobei in dem Co-Tensid der Formel (II) R1 eine ungesättigte Alkylgruppe mit 18 Kohlenstoffketten ist, und R2, R3 und R4 Hydroxylgruppen sind oder das Co-Tensid aus der Formel (II) ist, wobei R1 eine ungesättigte Alkylgruppe mit 22 Kohlenstoffketten ist, R2 und R3 Ethylhydroxygruppen sind und R4 eine Methylgruppe ist.
  7. Viskoelastisches Fluid nach einem der Ansprüche 1-6, wobei das Co-Tensid ausgewählt ist aus Talgtrimethylammoniumchlorid, Erucylamin (2)-ethoxylat, quartärem Ammoniumsalz oder einer Mischung davon.
  8. Viskoelastisches Fluid nach einem der Ansprüche 1-7, wobei die Konzentration des viskoelastischen Tensids in dem Fluidsystem von 0,5% bis 10 Gew.% beträgt und die Konzentration des Co-Tensids in dem Fluid von 0,1 Gew.% bis 4 Gew.% beträgt.
  9. Viskoelastisches Fluid nach Anspruch 1, wobei die Konzentration des viskoelastischen Tensids in dem Fluidsystem von 2% bis 8 Gew.%, vorzugsweise von 3% bis 5 Gew.% und die Konzentration des Co-Tensids in dem Fluid von 0,5 Gew.% bis 1,5 Gew.% beträgt.
  10. Zusammensetzung zur Bohrlochstimulation, umfassend von 0,5% bis 10% einer Mischung von wenigstens einem viskoelastischen Tensid und wenigstens einem synergistischen Co-Tensid, wobei das viskoelastische Tensid ein amphoteres Tensid der folgenden allgemeinen Formel (I) ist:
    Figure imgb0009
     wobei R1 eine gesättigte oder ungesättigte Kohlenwasserstoffgruppe mit 17 bis 29 Kohlenstoffatomen ist, R2 and R3 jeweils unabhängig ausgewählt sind aus einer geradkettigen oder verzweigten Alkyl- oder Hydroxyalkylgruppe mit 1 bis 6 Kohlenstoffatomen, R4 ausgewählt ist aus H, OH, Alkyl- oder Hydroxyalkylgruppen mit 1 bis 4 Kohlenstoffatomen; k eine ganze Zahl von 2-20 ist, m eine ganze Zahl von 1-20 ist und n eine ganze Zahl von 0-20 ist;
    und das synergistische Co-Tensid die folgende allgemeine Struktur (II) hat:
    Figure imgb0010
     wobei R1 eine gesättigte oder ungesättigte Kohlenwasserstoffgruppe mit 12 bis 22 Kohlenstoffatomen ist, R2, R3 und R4 jeweils unabhängig ausgewählt sind aus einer geradkettigen oder verzweigten Alkyl- oder Hydroxyalkylgruppe mit 1 bis 4 Kohlenstoffatomen und einer Hydroxylgruppe,
    wobei die Zusammensetzung zur Bohrlochstimulation eine Dichte von mehr als 1,14 g/cm3 hat.
  11. Fluid zur Bohrlochstimulation nach Anspruch 10, wobei das Fluid Folgendes ist: ein Bohrfluid, ein Komplettierungsfluid, ein Wiederaufwältigungsfluid, ein ansäuerndes Fluid, eine Kiespackung, ein Frakturierungsfluid, ein Matrix ansäuerndes Fluid, ein ansäuerndes Fluid zur Komplettierung, ein ansäuerndes Fluid zur Frakturierung oder ein ansäuerndes Fluid zum Entfernen einer Beschädigung, vorzugsweise ein Bohr-/Komplettierungsfluid ist.
  12. Ansäuerndes Fluid, das wenigstens eine Säure und das viskoelastische Fluid nach Anspruch 1 umfasst.
  13. Ansäuerndes Fluid nach Anspruch 12, wobei die Säure ausgewählt ist aus der Gruppe, bestehend aus Mineralsäuren, organischen Säuren und ihren Mischungen.
  14. Ansäuerndes Fluid nach Anspruch 13, wobei die Säure ausgewählt ist aus der Gruppe, bestehend aus Salzsäure, Fluorwasserstoffsäure, Essigsäure, Ameisensäure, Sulfaminsäure, Chloressigsäure und ihren Mischungen.
  15. Verfahren zur Frakturierung einer unterirdischen Formation, umfassend die Schritte des Pumpens des viskoelastischen Fluids nach einem der Ansprüche 1-10 durch ein Bohrloch und in eine unterirdische Formation mit einem Druck, der ausreicht, um die Formation aufzubrechen.
EP14709645.7A 2013-03-15 2014-03-12 Synergistische wirkung von co-tensiden auf die rheologische leistung von bohr-, komplettierungs- und frakturierungsflüssigkeiten Active EP2970744B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201361793695P 2013-03-15 2013-03-15
US201361861092P 2013-08-01 2013-08-01
PCT/EP2014/054759 WO2014140055A1 (en) 2013-03-15 2014-03-12 Synergistic effect of cosurfactants on the rheological performance of drilling, completion and fracturing fluids

Publications (2)

Publication Number Publication Date
EP2970744A1 EP2970744A1 (de) 2016-01-20
EP2970744B1 true EP2970744B1 (de) 2018-08-15

Family

ID=50272617

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14709645.7A Active EP2970744B1 (de) 2013-03-15 2014-03-12 Synergistische wirkung von co-tensiden auf die rheologische leistung von bohr-, komplettierungs- und frakturierungsflüssigkeiten

Country Status (7)

Country Link
US (1) US10308866B2 (de)
EP (1) EP2970744B1 (de)
BR (1) BR112015021194B1 (de)
CA (1) CA2904168C (de)
DK (1) DK2970744T3 (de)
RU (1) RU2691906C2 (de)
WO (1) WO2014140055A1 (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017074304A1 (en) 2015-10-26 2017-05-04 Halliburton Energy Services, Inc. Micro-proppant fracturing fluid compositions for enhancing complex fracture network performance
US10407606B2 (en) 2016-05-12 2019-09-10 Saudi Arabian Oil Company High temperature viscoelastic surfactant (VES) fluids comprising nanoparticle viscosity modifiers
US10047279B2 (en) 2016-05-12 2018-08-14 Saudi Arabian Oil Company High temperature viscoelastic surfactant (VES) fluids comprising polymeric viscosity modifiers
WO2018004593A1 (en) * 2016-06-30 2018-01-04 Halliburton Energy Services, Inc. Treatment fluids for stimulation of subterranean formations
MY197088A (en) * 2017-03-03 2023-05-24 Halliburton Energy Services Inc Lost circulation pill for severe losses using viscoelastic surfactant technology
US10947443B2 (en) 2017-03-03 2021-03-16 Halliburton Energy Services, Inc. Viscoelastic surfactant gel for perforation operations
US10563119B2 (en) 2017-07-27 2020-02-18 Saudi Arabian Oil Company Methods for producing seawater based, high temperature viscoelastic surfactant fluids with low scaling tendency
WO2023094434A1 (en) * 2021-11-23 2023-06-01 Nouryon Chemicals International B.V. Surfactant composition
US20230366296A1 (en) * 2022-05-12 2023-11-16 Baker Hughes Oilfield Operations Llc Methods for Transporting Scale Removal Agents into a Well
WO2024112840A1 (en) * 2022-11-23 2024-05-30 Energy Solutions (US) LLC Viscoelastic surfactant formulations and use in subterranean formations

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6258859B1 (en) * 1997-06-10 2001-07-10 Rhodia, Inc. Viscoelastic surfactant fluids and related methods of use
US6762154B2 (en) 2000-09-21 2004-07-13 Schlumberger Technology Corporation Viscoelastic surfactant fluids stable at high brine concentrations
US8785355B2 (en) * 2001-02-13 2014-07-22 Schlumberger Technology Corporation Viscoelastic compositions
US7148185B2 (en) 2001-12-03 2006-12-12 Schlumberger Technology Corporation Viscoelastic surfactant fluids stable at high brine concentration and methods of using same
US20060084579A1 (en) 2004-10-15 2006-04-20 Berger Paul D Viscoelastic surfactant mixtures
CA2628509C (en) * 2005-11-07 2014-07-29 Stepan Company Viscoelastic compositions comprising polycationic quaternary ammonium compounds
US7461694B2 (en) * 2005-11-16 2008-12-09 Rhodia Inc. Methods for recovering oil from an oil reservoir
US7556098B2 (en) * 2006-07-14 2009-07-07 Paul Daniel Berger Oil recovery method employing amphoteric surfactants
US9018146B2 (en) * 2006-11-22 2015-04-28 Baker Hughes Incorporated Method of treating a well with viscoelastic surfactant and viscosification activator
US20080277112A1 (en) * 2007-05-10 2008-11-13 Halliburton Energy Services, Inc. Methods for stimulating oil or gas production using a viscosified aqueous fluid with a chelating agent to remove calcium carbonate and similar materials from the matrix of a formation or a proppant pack
WO2009058589A2 (en) * 2007-10-31 2009-05-07 Rhodia Inc. Addition of zwitterionic surfactant to water soluble polymer to increase the stability of the polymers in aqueous solutions containing salt and/or surfactants
US7897547B1 (en) 2009-12-21 2011-03-01 Schlumberger Technology Corporation Viscoelastic surfactant rheology modifier
US8418761B2 (en) * 2010-07-29 2013-04-16 Halliburton Energy Services, Inc. Stimuli-responsive high viscosity pill
CN103649459B (zh) * 2011-05-13 2016-10-19 罗地亚管理公司 泡沫稳定性得到提高的应用及方法
CN103502386B (zh) * 2011-05-23 2017-03-08 阿克佐诺贝尔化学国际公司 增稠的粘弹性流体及其用途

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
DK2970744T3 (en) 2018-12-03
US10308866B2 (en) 2019-06-04
RU2015142821A (ru) 2017-04-20
CA2904168C (en) 2021-11-23
EP2970744A1 (de) 2016-01-20
RU2691906C2 (ru) 2019-06-18
WO2014140055A1 (en) 2014-09-18
CA2904168A1 (en) 2014-09-18
BR112015021194B1 (pt) 2021-09-21
US20160017210A1 (en) 2016-01-21
BR112015021194A2 (pt) 2017-07-18
RU2015142821A3 (de) 2018-03-19

Similar Documents

Publication Publication Date Title
EP2970744B1 (de) Synergistische wirkung von co-tensiden auf die rheologische leistung von bohr-, komplettierungs- und frakturierungsflüssigkeiten
DK1212385T3 (en) Quaternary ammonium salts as thickeners for aqueous systems
US6762154B2 (en) Viscoelastic surfactant fluids stable at high brine concentrations
EP1292651B1 (de) Viskoelastische oberflächenaktive itteln und zusammensetzungen die sie enthalten
US7207388B2 (en) Non-Damaging Fluid-Loss Pill and Method of Using the Same
RU2453576C2 (ru) Высокотемпературное гелирующее средство для модификации вязкости низко- и высокоплотных рассолов
EP2571957B1 (de) Erhöhung der viskosität viskoelastischer flüssigkeiten
CA2917622C (en) Composition for use in conducting downhole operations in oil and gas wells
AU2017401563B2 (en) Lost circulation pill for severe losses using viscoelastic surfactant technology
US9637681B2 (en) Agent for inhibiting the swelling of clays, compositions comprising said agent and methods implementing said agent
US20150344765A1 (en) Clay-swelling inhibitor, compositions comprising said inhibitor and processes using said inhibitor
US20050202978A1 (en) Polymer-based, surfactant-free, emulsions and methods of use thereof
WO2007065872A1 (en) High temperature gellant for viscosity modification of low and high density brines
US7358215B1 (en) Quaternary ammonium salts as thickening agents for aqueous systems
WO2023094434A1 (en) Surfactant composition

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20151001

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20160901

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

RIC1 Information provided on ipc code assigned before grant

Ipc: C09K 8/62 20060101ALI20180131BHEP

Ipc: C09K 8/68 20060101ALI20180131BHEP

Ipc: C09K 8/035 20060101AFI20180131BHEP

Ipc: E21B 43/26 20060101ALI20180131BHEP

Ipc: C09K 8/74 20060101ALI20180131BHEP

Ipc: C09K 8/60 20060101ALI20180131BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20180323

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

GRAL Information related to payment of fee for publishing/printing deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR3

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAR Information related to intention to grant a patent recorded

Free format text: ORIGINAL CODE: EPIDOSNIGR71

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

INTC Intention to grant announced (deleted)
AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

INTG Intention to grant announced

Effective date: 20180709

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: GB

Ref legal event code: FG4D

Ref country code: AT

Ref legal event code: REF

Ref document number: 1029736

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180815

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602014030398

Country of ref document: DE

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

Effective date: 20181126

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20180815

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: NO

Ref legal event code: T2

Effective date: 20180815

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1029736

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180815

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181116

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181115

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181215

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602014030398

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20190516

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190312

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190312

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190331

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190331

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602014030398

Country of ref document: DE

Representative=s name: LKGLOBAL LORENZ UND KOPF PATENTANWALT, ATTORNE, DE

Ref country code: DE

Ref legal event code: R082

Ref document number: 602014030398

Country of ref document: DE

Representative=s name: LKGLOBAL | LORENZ & KOPF PARTG MBB PATENTANWAE, DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190312

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181215

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20140312

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180815

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NO

Payment date: 20230329

Year of fee payment: 10

Ref country code: DK

Payment date: 20230329

Year of fee payment: 10

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230515

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240327

Year of fee payment: 11

Ref country code: GB

Payment date: 20240327

Year of fee payment: 11